Dyeing keratinaceous material with n-carbamoylethyl amines

ABSTRACT

Method of dyeing keratinaceous material such as hair or fur by contacting same with an N-carbamoylethyl aromatic amine of the formula WHERE Ar is benzene, biphenyl or naphthalene; R1 is 2carbamoylethylamino or bis(2-carbamoylethyl)amino; R2 is amino, nitro, hydroxy or R1; and R3 is amino, nitro, hydrogen, halo, lower alkyl, lower alkoxy or R1; or acid addition salts thereof. The invention also includes compositions containing the Ncarbamoylethyl aromatic amines.

United States Patent Paul DYEING KERATINACEOUS MATERIAL WITHN-CARBAMOYLETHYL AMINES Albert Peter Paul, Teaneck, NJ.

American Cyanamld Company, Stamford, Conn.

May 16, 1969 825,428

Inventor:

Assignee:

Filed:

Appl. No.:

US. Cl ..8/10, 8/11, 260/558,

260/559 Int. Cl. ..D06p 3/04, D06p 3/08 Field of Search ..8/l0, l 1;260/558, 559

References Cited UNITED STATES PATENTS 4/1944 Dickey ..260/205 l/ l 9642/1966 1/1969 Seemuller Bartoszewicz ..8/1 1 X Primary Examiner-GeorgeF. Lesmes Assistant Examiner-Patricia C. lves Attorney-Patrick C. Baker[5 7] ABSTRACT Method of dyeing keratinaceous material such as hair orfur by contacting same with an N-carbamoylethyl aromatic amine of theformula 7 Claims, No Drawings DYEING KERATINACEOUS MATERIAL WITH N-CARBAMOYLETHYL AMINES This invention relates to a method and tocompositions for dyeing fibrous materials, particularly keratinaceousmaterials such as animal and human hair, wherein the method comprisesapplying to said materials an N-carbamoylethyl aromatic amine, orcomposition containing same, of the formula where Ar is benzene,biphenyl or naphthalene; R is 2-carbamoylethylamino orbis(2-carbamoylethyl)amino; R is amino, nitro, hydroxy or R; and R isamino, nitro, hydrogen, halo, lower alkyl, lower alkoxy or RHThecompounds of this invention also include the acid addition salts ofcompounds of the above formula, including organic and inorganic acidaddition salts. The inorganic acids are preferred, typical examplesbeing sulfuric, hydrochloric, phosphoric, nitric, and boric. Organicacids include both the monoand polycarboxylic acids such as formic,acetic, propionic, capric, stearic, benzoic, malonic, succinic, andphthalic.

A related application field on the same day U.S. application Ser. No.825,434, filed May 16, 1969, now abandoned discloses and claims theabove-described aromatic amines and salts, and a second application U.S.application Ser. No. 825,427, filed May 16, 1969, also filed on the sameday, covers a preferred method of preparing the above compounds.

The compounds of Formula I or salts thereof may be prepared by at leastthree methods. In the first method an aromatic amine or aromaticnitroamine is reacted with acrylamide in acetic acid (dilute or glacial,-100 percent) at an elevated temperature, preferably from about 50C. toabout 120C., to give a product wherein one or more of the amino hydrogenatoms is replaced by a carbamoylethyl group.

In a second method, an aromatic nitroamine is reacted with acrylamide atabout C. to 145C. in a polar, non-hydroxylated solvent such asdimethylformamide and in the presence of a basic catalyst having a pK(negative logarithm of the basicity dissociation constant) of less than10 to give a product having a nitro group and at least one propionamidegroup. Typical of the basic catalysts are quaternary ammonium hydroxidessuch as benzyl trimethyl ammonium hydroxide and alkali metal alkoxidessuch as sodium or potassium tertiary butoxide or methoxide. The basiccatalyst is employed in catalytic amounts such as 0.01 0.5 mol ofcatalyst per mol of aromatic nitroamine reactant, preferably 0.02 0.04mol, same basis. This method is the subject of a copending applicationfiled on the same day as the present application under the name ofRichard Boardman Toothill, US. application Ser. No. 825,427.

In a third method, the nitro-substituted products may be prepared fromthe corresponding haloand nitro-substituted aromatic compounds byreaction with aminopropionamide or iminobispropionamide in a loweralkanol such as ethanol in the presence of a weak base such as sodiumbicarbonate, pyridine or triethanolamine. The reaction is conducted atelevated temperature, preferably reflux, and the aminopropionamide oriminobispropionamide group replaces the halo group.

In the second method of preparation, where the starting material is anaromatic nitro diamine or aminonitrophenol, a lower alkanol such asethanol is also present and the reaction temperature is from about 60C.to reflux.

In the first and second above methods, one or both hydrogen atoms on theamino groups of the starting material are replaced by one or twocarbamoylethyl groups to give one to three monoor di-carbamoylethylgroups in the product. The number of such groups in the product willdepend, of course, on variables such as the number of amino and othergroups in the reactant, mol ratios of reactants, and conditions oftemperature and reaction medium. One exception to this generalizationoccurs when the reactant contains a single amino group and a singlenitro group. In this instance the nitro bispropionamide product resultsonly by the second method above.

In the third method of preparation, those reactants in which the halogroup is ortho or para to the nitro group are preferred. Here again thedegree of aminopropionamide or iminobispropionamide substitution willdepend on choice of starting material (the number of active halogenatoms), reactant mol ratios, and other reaction conditions, except asdescribed above.

Where the product of the three methods described above contains at leastone nitro group, one or more of the nitro groups may be reduced to aminoby known procedures such as reaction at superatmospheric pressures overpalladium on carbon in ethanol.

As noted above, the type and degree of substitution in the compounds ofthe invention will depend primarily on choice of reactants and reactantmol ratios. Thus, the relationship of R R and R may be ortho, meta, orpara, or any combination thereof, with those limitations readilyapparent to the skilled chemist. Regarding their utility as dyes forkeratinaceous materials, however, those compounds are preferred in whichR and R are ortho or para.

Representative of the aromatic nitroamine reactants useful in preparingthe compounds of the invention are the following: anilines such as2-nitro, 3-nitro, 4-nitro, 2- or 3-chloro-4- nitro-, 2- or3-methyl-4-nitro, 2- or 3-methoxy-4-nitro, and 2,4-dinitro-aniline;naphthylamines such as l-amin0-2-nitro-, 2-amino-l-nitro-,2-amino-3-nitro-, l-amino-8-nitro-, and lamino-2,4-dinitro-naphthalene;and biphenylamines (xenylamines) such as 2-amino-2'-nitro-,4-amino-4-nitro-, 4- amino-3-nitro-, and4,4-diamino-3,3-dinitro-biphenyl.

Representative aromatic polyamine reactants are the following: ortho orpara phenylenediamines such as 1,2- diaminobenzene, 1,3-diaminobenzene,1,4-diaminobenzene, l ,4-diamino-2-methylbenzene,l,4-diamino-2-methoxybenzene, 2-chloro-1,4-diaminobenzene,1,4-diamino-2- nitrobenzene; diaminonaphthalenes such as l,2-diamino-,1,4- diamino-, l,8-diamino-, 2,3-diamino-, 2,6-diamino-, 1,4-diamino-2-nitro, and biphenylamines such as 2,2'-diamino-,4,4'-diamino-, 4,4-diamino-3,3'-dinitro-, 3,4-di-amino and 3,3',4,4.Typical aromatic hydroxy amine reactants are the following: aminophenolssuch as 2(or 3%aminophenol. 2.

amino-4-methyl-2amino-4(or 5)-nitrophenol. 4-aminophenol, 4-amino'2(or3)-chlorophenol. 4-amino-2(or 3l-methoxyphenol, and 4-ar n ino 2 (or 3methylphenol; aminafaphThols such as l-amino-S-(or 8)-hydroxynaphthaleneand 2-amino- 1( or 3)-hydroxynaphtha-lene; and hydroxyphenylamines suchas 4-amino-4-hydroxybiphenyl and 4-amino-2-hydroxybiphenyl.

It is often desirable to isolate the compounds of Formula I above asacid addition salts since the salts tend to be more stable to airoxidation, particularly where the products have one or more amino groupsor an hydroxyl group. This is done after carbamoylethylation is completeand after the product has undergone further reduction to the extentintended, by clarifying the solution of the final product, and addingdilute or concentrated mineral acid, preferably hydrochloric o 'sulfuricGiven the above description, the remaining details of the methods ofpreparation will be readily apparent. For example, conditions such asequivalent solvents and catalysts, order of addition, concentration ofreactants and catalysts in the reaction medium, temperature, pressure,workup and isolation procedures, are routine. Likewise, the startingmaterials are known and, for the most part, commercially available.

The compounds of this invention are useful as dyestuffs, particularlyfor dyeing keratinaceous materials. In regard to the dyeing ofkeratinaceous fibers, particularly human hair, the compounds comprisetwo classes: direct dyes and oxidation dyes. Those compounds wherein atleast one of R and R is nitro are direct dyes; those compounds devoid ofnitro groups or wherein at least one of R and R is amino or hydroxy] areoxidation dyes or oxidation dye modifiers. Compounds containing both anitro group and an amino or hydroxyl group impart color directly.

The hair dye utility of the compounds of this invention is based notonly on the ability of these compounds to impart a wide variety ofcolors to hair, depending on the compound employed or upon combinationwith known color modifiers, but also on other required properties whichthey possess such as the following: solubility or dispersibility in awide variety of cosmetic vehicles, substantivity to the hair,substantially no tendency to sublimation on the hair, substantialstability in dye baths, dyeability at ambient temperature, uniform andlevel dyeing properties, and good reproducibility of dyeing propertiesincluding color fastness and wear fastness. The oxidation dye compoundsof this invention are superior to the many N- alkylated derivatives ofphenylenediamine compounds whether used alone or in mixtures withcommercially available oxidation dyes or modifiers. Likewise, the directdyeing compounds of this invention have properties superior to nitro andother direct hair dyes, have better solubility, provide brilliantcolors, dye rapidly and level, and are useful whether the hair bevirgin, bleached or permanently waved.

Especially noteworthy properties of these compounds are the variety anddepth of colors they can impart to hair and the lightfastness of thecolors. The superior lightfastness is discernible even when thecompounds are admixed with commercial hair dyes. These properties appearto result primarily from the presence of the N-carbamoylethylamino groupin the compounds, although they are enhanced by the presence of theother groups defined by R and R since these groups (except hydrogen) areknown chromophores or auxochromes. indeed, the dye chemist, given thepresent disclosure, can easily substitute many other known chromophoreand auxochrome groups for those defined by R and R. For example,chromophore groups generally contain electronegative atoms or groups ofatoms and include groups containing sulfonyl, carbonyl, thiocarbonyl,azo, and groups containing ethylenically unsaturated carbon atoms.Similarly, the dye chemist would know how to substitute on the aromaticring other auxochrome (electron donating) groups such as primary andsecondary amino, alkoxy, aryloxy, or aralkyloxy groups.

The compounds of formula (l) may be admixed with a wide variety of knownmaterials and applied to the hair by known methods to achieve superiordyeing effects. For example, the compounds which operate as oxidationdyes may be dissolved in a suitable aqueous medium, which may containingredients listed below, and adjusted to the desired pH. The resultingcomposition is then mixed with about equal parts of a peroxide solutionsuch as 6 percent hydrogen peroxide or solutions of equivalent strengthcontaining urea peroxide, melamine peroxide, or persalts such asbromate, perborate, percarbonate, or persulfate. Depending on theperoxide concentration and pH, the resulting composition will bleach aswell as dye the hair.

The dye solution may also contain other ingredients commonly employed inthe dyestuffs art. These include nontoxic organic solvents miscible withwater such as benzyl, ethyl and isopropyl alcohols; stabilizers againstair oxidation such as sodium sulfite; emulsifiers and surfactants fordye solubilization and color absorption; opacifying and thickeningagents; and color modifiers.

The color modifiers encompass the whole field of known oxidation anddirect dyes. Included among the known oxidation dye color modifiers arethe phenols (amino-, nitroor polyhydroxy phenols) such as pyrogallol,hydroquinone, phydroxy anisole, resorcinol, phloroglucinol,pyrocathechol, 2,4-dinitrophenol, o-aminophenol, m-aminophenol,paminophenol, 2,4-diaminophenol, 2,6-diaminopyridine, hydroxy pyridine,m-diamino anisol sulfate, and the like; and aromatic diamines such aso-, mand p-phenylene diamine, 2,4-diaminoanisole, o-nitro-p-phenylenediamine, p-toluylene diamine, and the like.

The compounds of formula (I) may be employed singly or in admixture,with or without one or more of the known color modifiers and otheradditives, to give the desired tones. The compounds are effective ashair dyes over a wide pH range, from about 2 to about 12, but a pH of atleast about 7 is preferred, more particularly in the range of from about7.5 to about 10. Any water-dispersible basic material which iscompatible with the balance of the dye composition may be employed, inan amount which will provide the desired pH. Ammonium hydroxide ispreferred but other basic compounds are useful, such as the alkali andalkaline earth metal hydroxides, carbonates or bicarbonates; amines suchas primary aliphatic diamines (ethylenediamine, LZ-diaminQpropane. andthe like), alkanolamines (ethanolamine. diethanolamine. and the like),and heterocyclic amines (morpholine. piperidine. piperazine, and thelike). The pH may also be adjusted with acidic compounds, includingorganic or inorganic acids or salts thereof, such as sulfuric, formic,acetic or citric acid, ammonium sulfate, sodium dihydrogen phosphate, orpotassium bisulfate.

The following examples are intended as further illustration of theinvention and are not necessarily limitative. All parts and percentagesare by weight unless otherwise specified.

EXAMPLE 1 3-p-Nitroanilinopropionamide l NHCHaCHlC ONHz To 100 ml.glacial acetic acid is added in portions, 13.8 g. (0.1 mole)p-nitroaniline and 7.1 g. (0.1 mole) acrylamide. After completion ofaddition the solution is stirred at C. for 10 hours and ambienttemperature for 1 hour. The solution is poured with stirring into 1500ml. water. The precipitate is collected by filtration, washed with 500ml. water and dried in a steam oven to yield 12.6 g. of crude product.Removal of unreacted p-nitroaniline is effected by leaching severaltimes with small portions of ethyl acetate and yields 5.5 g.3-pnitroanilinopropionamide, a yellow product, melting at l7l.5l73C.

When this product is applied to albino, bleached or permanently wavedhair from an alkaline vehicle in a concentration of 0.5 percent, abright yellow shade is obtained after 10 minutes at ambient temperature.

EXAMPLE 2 3-(p-aminoanilino )propionamide ILHCHzCHrCONH:

To a Parr bottle kept in a nitrogen atmosphere is added 200 mg. 10percent Pd/C (palladium on carbon) catalyst which is immediately coveredwith 20 ml. ethanol. A warm slurry of 12.0 g. (0.057 mole)3-p-(nitroanilino)propionamide (such as prepared in Example 1) in 200ml. ethanol is added. Reduction is carried out on a Parr shaker at 40psi of hydrogen without heating. Theoretical hydrogen take-up isaccomplished within two hours. The catalyst is removed by gravityfiltration followed by vacuum filtration through a hyfio cake. Thefiltrate is taken to dryness on a rotary evaporator to yield 9.0 g.3-(p-aminoanilino)propionamide, tan crystals, melting at 94-95.5C.

Dissolved in an alkaline vehicle, in which it has very good solubility,in a concentration of 4 percent and applied to virgin, bleached orpermanently waved hair, a black shade with a slight brown hue isobtained. Swatches of hair thus dyed have excellent light stabilityafter days of exposure to sunlight. The addition of a small quantity ofp-hydroxyanisole, or 2,6- diaminopyridine in the presence of2,5-dinitrophenol, results in a jet black shade of excellent lightstability. Compounding with p-phenylenediamine results in a warm brownshade.

EXAMPLE 3 3,3-(p-Nitrophenylimino)bispropionamide To 50 ml.dimethylformamide is added in portions, 27.6 g. (0.2 mole)p-nitroaniline, 28.4 g. (0.4 mole) acrylamide and 200 mg.potassium-t-butoxide. After stirring 18 hours at ambient temperature,the solution is poured into 1500 ml. water. The precipitate is collectedby filtration, washed with 500 ml. water and dried in a steam oven.Removal of unreacted pnitroaniline is effected by leaching several timeswith small portions of ethyl acetate to yield 26.0 g.3,3'-(p-nitrophenylimino)bispropionamide, a yellow powder, melting at201.5-203C. When applied to hair a yellow shade similar to but not asstrong as that of Example 1, is obtained.

EXAMPLE 4 3 ,3-(p-Aminophenylimino)bispropionamide IIIH:

I N(CHzCHzCONH2)2 To a Parr bottle kept in a nitrogen atmosphere isadded 200 mg. 10 percent Pd/C catalyst which is immediately covered withml. anhydrous methanol. A warm slurry of 10.0 g. (0.036 mole)3,3'-(p-nitrophenylimino)bispropionamide in 200 ml. purified methanol isadded. Reduction is carried out on a Parr shaker at 40 psi of hydrogenwithout heating. Theoretical hydrogen takeup is accomplished within 2hours. The catalyst is removed by gravity filtration followed by vacuumfiltration through a filter aid. The filtrate is taken to dryness on arotary evaporator to yield 7.0 g.3,3-(paminophenylimino(bispropionamide, tan crystals, melting atl40-141C.

EXAMPLE 5 3,3 '-(p-Phenylenediimino)bispropionamide r mcmomc onm INHCHzGHzCONHz To 100 ml. ethanol under nitrogen is added in portions10.8 g. (0.1 mole) p-phenylenediamine, 15.6 g. (0.22 mole) acrylameltingat 163-165C. When applied to albino hair in an a1- kaline vehicle, ayellow shade of medium depth is obtained.

EXAMPLE 6 3 ,3'-(p-Phenylenedinitrilo )tetrakispropionamideltHUllzCllzCONll-z):

l muuivutuommi To 25 ml. ethanol and ml. glacial acetic acid undernitrogen is added 108 g. (0.1 mole) p-phenylenediamine and 28.4 g. (0.4mole) acrylamide. The solution is heated to C. under nitrogen for 6hours and stirred at ambient temperatures for 1 hour. Dimethylformamide,ml. is added. The solution is poured into 1500 ml. isopropanol withstirring. The precipitate is collected by filtration, washed withisopropanol and dried without heat in vacuo to yield 20.5 g.3,3-(p-phenylenedinitrilo)tetrakispropionamide, lavender crystals,melting at 196-197C.

EXAMPLE 7 3-( 4-Amino-3-nitroanilino )propionamide ITIH:

l NHCIIQCHQCONH:

To 100 ml. ethanol is added 13.9 g. (0.1 mole)2-nitro-pphenylenediamine, 7.1 g. (0.1 mole) acrylamide and 10.0 ml.glacial acetic acid. The solution is heated at reflux for 18 hours, andstirred without temperature control for 1 hour; the product is collectedby filtration and washed with carbon tetrachloride. It is dried withoutheat in vacuo to yield 12.1 g. 3-(4-amino-3-nitroanilino)propionamide,as red-brown crystals, melting at 144.5l46.5C. When applied to albino,virgin, bleached and permanently waved hair from alkaline medium, in 0.5percent concentration, for 10 minutes at ambient temperature, an intensebluish-red shade is obtained. This compound has excellent levellingproperties.

EXAMPLE 8 3,3'-(4-Amino-3-nitrophenylimino)bispropionamide To 100 ml.ethanol is added 13.9 g. (0.1 mole) 2-nitropphenylenediamine, 28.4 g.(0.4 mole) acrylamide and 10.0 ml. glacial acetic acid. The solution isheated at reflux for 24 hours and stirred at ambient temperature for 1hour. The product is collected by filtration, washed with carbontetrachloride and dried without heat in vacuo to yield 10.5 g.3,3'-(4-amino-3-nitrophenylimino)bispropionamide, as redbrown crystals,sinters at 210C, melting at 2l4-215C.

When applied to hair, in a manner similar to the compound of Example 7,a similar shade but not as strong, is obtained.

EXAMPLE 9 3-p-Hydroxyanilinopropionamide hydrochloride l IICl-NHCHzClIzCONHz To a mixture of 150 ml. ethanol and 15 ml. glacial acetic acid isadded 32.7 g. (0.3 mole) p-aminophenol and 21.3 g. (0.3 mole)acrylamide. The whole is heated at reflux under nitrogen for 18 hours.It is cooled to ambient temperature, acidified with concentratedhydrochloric acid and filtered. The product is washed with ethanol anddried. Yield is 24.9 g., melting at l86187C. On recrystallization frommixed ethanol and ethyl acetate it melts at l94.5-195C.

EXAMPLE l 3 ,3 -(p-Hydroxyphenylimino)bispropionamide EXAMPLE 1 l3-(4-Nitro-o-toluidino)propionamide IIIHCHzCHrC ONH:

CII;

To 40 ml. dimethylformamide is added in portions, 7.6 g. (0.05 mole)2-methyl-4-nitroaniline, 3.6 g. (0.05 mole) acrylamide and 200 mg.potassium-t-butoxide. After addition is complete the solution is stirredat reflux for 6 hours. It is poured with stirring into 1500 ml. water.The precipitate is collected by filtration, washed with 500 ml. waterand dried in a steam oven to yield 3.9 g. of crude product. Separationof 3- (4-nitro-o-toluidino)propionamide from starting material andby-products is effected by column chromatography. The chromatographysystem used is as follows: 100 g. silica gel packed in benzene. Elutedwith 1:1 ethyl acetate-benzene, benzene, 1 l0 chloroform-benzene, 1:1chloroform-benzene, chloroform, 1:1 ethyl acetate-chloroform, ethanol.From the column 0.49 g. of 3-(4-nitro-o-toluidino)propionamide isobtained, as a yellow powder, melting at l65.5167.0C.

EXAMPLE l2 3-(4-Nitro-o-anisidino)propionamide lIIIICHsCHzCONHz Amixture of 33.6 g. (0.2 mole) 4-nitro-o-anisidine, ml. glacial aceticacid, 15.6 g. (0.22 mole) acrylamide, 0.5 g. cupric acetate and 0.1 g.hydroquinone, is heated at reflux for 6 hours, cooled to roomtemperature overnight and filtered. The solids are recrystallized fromacetone-benzene mixtures to yield 41 g. 3-(4-nitro-o-anisidino)propionamide as a yellow crystalline solid, melting at l57l57.5C.

EXAMPLE l3 3-( 2-Chloro-4-nitroanilino )propionamide IIIIICHzClIzCONlhTo 40 m1. dimethylformamide is added in portions, 8.6 g. (0.05 mole)2-chloro-4-nitroaniline, 7.1 g. (0.05 mole) acrylamide and 200 mg.potassium-t-butoxide. After heating at the reflux for 4 hours, thecooled solution is poured into 1500 ml. water. The precipitate iscollected by filtration, washed with 500 ml. water and dried in a steamoven to yield 10.2 g. crude product. A 2.0 g. sample is recrystallizedfrom water, then ethanol, to yield 1.4 g. of 3-( 2-chloro-4-nitroanilino)propionamide, as a yellow powder, melting at 147.5-l48.5C.

EXAMPLE 14 3-( 2,4-Dinitroanilino)propionamide lIlHCHzCHzc ONH:

To ml. dimethylformamide is added 45.5 g. (0.25 mole)2,4-dinitroaniline, 18.0 g. (0.25 mole) acrylamide and 500 mg.potassium-t-butoxide. After heating at the reflux for 8 hours, thecooled solution is poured into 2000 ml. benzene, stirred for 1 hour,filtered, washed with 500 ml. benzene and dried in a steam oven to yield34.0 g. crude product. A 2.0 g. sample after recrystallization fromethanol-ethyl acetate, yields 1.5 g. 3-(2,4-dinitroanilino)propionamide,a yellow powder, melting at l23124.5C.

EXAMPLE 15 3-(4-Nitrol -naphthylamino)propionamide lfHCHzCHaCONH:

To 50 ml. dimethylformamide is added 18.8 g. (0.1 mole) lamino-4-nitronaphthalene, 7.1 (0.1 mole) acrylamide and EXAMPLE 16 3-(4'-Nitro-4-biphenylylamino)propionamide if in Example 15, 0.1 mole ofl-amino-4-nitronaphthalene is replaced with 21.4 g. (0.1 mole)4-a'mino-4-nitrobiphenyl and the rest of the procedure of Example l5followed, the product obtainedis-3-(4'-nitro-4-biphenylylamino)propionamide. Doubling the proportionof acrylamide provides the 3 ,3 4 '-nitro-4-pheny|yl )imino]bispropionamide. Using the procedure of Example 2, the nitro group ineither compound is reduced to an amino group to provide3-(4-aminobiphenylylamino)propionamide and3,3-[(4'-amino-4-biphenylyl)iminolbispropionamide, respectively.

EXAMPLE 1 7 3.-( 3-Nitro-p-toluidino )propionamide GIH;

1 NHCHzCHgG ONH,

To a mixture of 80 ml. toluene and ml. glacial acetic acid is added 30.4g. (0.2 mole) 3-nitro-p-toluidine. The mixture is taken to reflux withstirring and a solution of 15.64 g. (0.22 mole) acrylamide in acetone isadded over 1.5 hours. The acetone is allowed to distill 'as it is beingadded. An additional 100 ml. toluene is then added and the reaction isstirred at reflux for 2 hours, cooled to room temperature andchromatographed on a short alumina column. The first fraction isdiscarded and the second fraction on evaporation results in 7.0 g. of3(3-nitro-p-toluidino)propionamide, a yellow powder, melting at 1 185C.

EXAMPLE l8 3-( 3-Amino-p-toluidino)propionamide dihydrochloridep-toluidino)propionamide dihydrochloride, a white powder,

melting at 222C. (dec.).

EXAMPLE 19 3-( 5-Nitro-o-toluidino)propionamide The above compound isprepared substantially as described in Example 17 except thatS-nit'ro-o-toluidine is substituted for the 3-nitro-p-toluidine. Thecompound melts at l68l 69.5C.

EXAMPLE 20 3-( 5-Amino-o-toluidino)propionamide dihydrochloride NHz If,in Example 18, one substitutes an equal quantity of 3-( 5-nitro-o-toluidino)propionamide for3-(4-methyl-3nitrophenyl)propionamide, there is obtained 5.26 g. of3-(5-amino-otoluidino)propionamide dihydrochloride as a white powder,melting at 207.5208.5C.

EXAMPLE 21 3-( S-Nitro-o-anisidino )propionamide To a refluxing mixtureof 33.6 g. (0.2 mole) 2-amino-4-nitro anisole and ml. glacial aceticacid, is added 15.6 g. (0.22 mole) acrylamide in portions over 15minutes. After heating at the reflux for an additional hour, thereaction mixture is treated with activated carbon, filtered, andevaporated under vacuum to the point of crystallization. The product isrecrystallized from acetone to yield 6.9 g.3-(5-nitro-oanisidino)propionamide, a yellow crystalline solid, meltingat l59-l60C.

EXAMPLE 22 3-( 5-Amino-o-anisidino)propionamide dihydrochloride I NH:

If, in Example l8,one substitutes 29 g. of3-(5-nitro-oanisidino)propionamide for 3-(4-methyl-3-nitrophenyl)-propionamide, there is obtained 14.68 g.3-(5-amino-oanisidino)-'propionamide dihydrochloride as a white powder,melting at 199200C. (dec.

EXAMPLE 23 3-(2-Amino-4-nitroanilino )propionamide EXAMPLE 243-(4-Amino-o-toluidino)propionamide dihydrochloride HNCHrCHzQONHz If inExample 18 one substitutes an equal quantity of 3-(4-nitro-o-toluidino)propionamide for3-(4-methyl-3-nitrophenyl)propionamide, then there is obtained 8.7 g. of3-(4-aminoo-toluidino)propionamide dihydrochloride as a white powder,melting at 206C. (dec.

EXAMPLE 25 3-[ 4-Aminol -naphthyl)amino1propionamide dihydrochloride lHNCHzCI-IzC ONH:

lf in Example 18, one substitutes 2.2 g.3-(4-nitro-lnaphthylamino)propionamide for3-(4-methyl-3-nitrophenyl)-propionamide, there is obtained 2 g.3-[(4-amino-1- naphthyl)-amino]propionamide dihydrochloride, as a whitepowder, melting at 290C. (dec.

EXAMPLE 26 3 ,3 3-Nitro-p-tolylimino)bispropionamide IIKCHzCHzCONHzM IOH;

To a refluxing mixture of 7.1 g. (0.047 mole) 3-nitro-ptoluidine and 25ml. acetic acid is added 3.91 g. (0.055 mole) acrylamide in portionsover 1.5 hours. After heating at reflux for an additional 30 minutes,the reaction mixture is poured over ice, neutralized with 200 ml. 5Ncaustic and extracted with 1 liter of chloroform. The aqueous layer isfiltered and the solids recrystallized from acetone to yield 0.050 g.3,3'-(3- nitro-p-tolylimino)bispropionamide as a pale yellow solid,melting at l97l98C.

EXAMPLE 27 3,3-( 2-Methoxy-5-nitrophenylimino)bispropionamide A mixtureof 33.6 g. (0.2 mole) S-nitro-o-anisidine, ml. benzene, 10 ml. aceticacid, 15.6 g. (0.22 mole) acrylamide and 2 drops of concentratedsulfuric acid are stirred at ambient temperature, then taken to refluxfor 30 minutes. After cooling to 50C. the solids are filtered, washedwith benzene and recrystallized from acetone to yield 3.95 g. 3,3-(2-methoxy-S-nitrophenylimino)bispropionamide, a yellow crystalline solid,melting at l32133C.

EXAMPLE 28 3-( 2-l-lydroxy-4-nitroanilino )propionamide NHCH CHrC ONHz Amixture of 30.8 g. (0.2 mole) 2-amino-5-nitrophenol, 200 ml. toluene,15.6 g. (0.22 mole) acrylamide, 20 mg. hydroquinone and 5 drops ofconcentrated sulfuric acid is heated at reflux for 45 minutes. Thesolids are filtered hot, washed with benzene and dried under vacuum toyield 46.5 g. 3-(2-hydroxy-4-nitroanilino)propionamide, a yellow solid,melting at 208.5209C.

EXAMPLE 29 3-(4-Amino-2-hydroxyanilino )propionamide dihydrochlorideNHCHQCHQCONHI HgN I 2H Cl If, in Example l8, one substitutes an equalquantity of 3-( 2- hydroxy-4-nitroanilino)propionamide for3-(4-methyl-3-nitro phenyl)propionamide, there is obtained 11.71 g. of3-(4- amino-2-hydroxyanilino)propionamide dihydrochloride, as a whitesolid, melting at 222C. (dec.).

EXAMPLE 3O 3-( 4-Hydroxy-3-nitroanilino)propionamide I NHCHZCHQCONHi If,in Example 28, one substitutes an equal quantity of 4-amino-Z-nitrophenol in place of 2-amino-5-nitro phenol, then there isobtained 10 g. 3-( 4-hydroxy-3-nitroanilino)propionamide as a yellowsolid, melting at l68l69C.

EXAMPLE 3! 3-( 3-Amino-4hydroxyanilino)propionamide dihydrochloride lNrrcmcmconm If in Example 18, one substitutes g. 3-(4 -hydroxy-3-nitro 1anilino)propionamide for 3-(4-methyl-3-nitro ph'enyl)propionamide, thereis obtained 5.88 g. 3-(3-amino-4- hydroxy anilino)propionamidedihydrochloride, a white powder, melting at 231C. (dec.).

EXAMPLE 32 3-(oHydroxyanilino)propionamide NHCHzCHzC.ONH2

If in Example 28, one substitutes 32.7 g. o-amino phenol for2-amino-5-nitro phenol and uses 23.5 g. acrylamide and 150 ml. toluene,there is obtained 3 g. 3-(o-hydroxyariilino) propionamide as an offwhite solid, melting at 93.5-94 "C.

EXAMPLE 33 3-(2,4-Diaminoanilino)propionamide m tomomcomiq l If inExample 2, one substitutes 10 g. 3-(2,4- dinitroanilino)propionamide for3-(p-nitroanilino)propionamide, there is obtained 5.5 g. 3-(2,4-diaminoanilino)propionamide, as an off-white solid, melting at 127.5-129c.

EXAMPLE 34 I 3-( 3,4-Diaminoanilino)propionamide dihydroch lorideNHCHaCHzCQNHg 2HCl l lHz If in Example l8, one substitutes an equalquantity of 3-(4- amino-3-nitroanilino)propionamide for 3-(4-methyl-3-nitrophenyl)propionamide, there is obtained 11.6 g. of 3-(3,4-diaminoanilino)propionamide dihydrochloride, a White solid.

EXAMPLE 35 3-(4-Amino-o-anisidino)propionamide dihydrochlorideamomomoonm -2HG1 HgN if in Example l8, one substitutes 5.15 g.3-(4-nitro-oanisidino)propionamide for3-(4-methyl-3-nitrophenyl)propionamide, there is obtained 5.75 g.3-(4-amino-oanisidino)propionamide dihydrochloride, a white solid,melting at 184C. (dec.).

EXAMPLE 36 l NHZ A mixture of l g. 5 percent platinum on carbon, 10 ml.concentrated hydrochloric acid, 200 cc. alcohol and 12.7 g. (0.05 mole)3-(2,4-dinitro anilino)propionamide is shaken in a Parr Apparatus for 3hours; the solids are filtered and washed with isopropanol and acetone.The solids are dissolved in 250 ml. water, basified with concentratedammonium hydroxide, filtered, dried and recrystallized from acetone toyield 5.03 g. 3- (4-amino-2-nitroanilino)propionamide as a reddish browncrystalline solid, melting at 205-206C.

EXAMPLE 3 7 3-(4'-Amino biphenylylamino)propionamide If in Example 2,one substitutes 5 g. 3-(4'-nitro-4-biphenylamino)propionamide for3-(p-nitroanilino)propionamide, there is obtained 2.54 g. of 3-(4'-aminobiphenylamino)propionamide as an off-white solid, melting at l76.5177C.

EXAMPLE 38 Utility as Oxidation Dye A. A dye composition is prepared asfollows:

To 54.9 parts water is added 10 parts of the non-ionic dispersing agentisooctylphenyl(polyethoxy)ethanol, 0.] part sodium sulfite and 4 partslauric acid diethanolamide. The whole is heated with stirring to 70C.during which 6 parts 3-(p-amino-anilino)propionamide (Example 2) isadded. When solution of the dye is complete, the whole is cooled to 35C.with stirring. To the solution of the dye is added 10 parts isopropanol,10 parts oleic acid and 5 parts 28 percent ammonium hydroxide solution.

B. One part dye composition of A" above is mixed with an equal part of 6percent hydrogen peroxide solution.

C. Yellowish grey hair is contacted with the mixture of the compositionof B without delay at ambient temperature for 20 to 30 minutes. The hairis then thoroughly rinsed, washed with a dilute shampoo and dried. Theresult is a deep brownblack uniform color of good fastness to light.

When the above procedure is applied to other compounds of the foregoingexamples, the following results are obtained:

Compound of Example Color of Dyed Hair 4 grey 5 yellow 9 light brown2+20(or 22) blue 2+29 brown 2+3 l(or 32) brown 33 green 34 green EXAMPLE39 Utility as Direct Dye A dye composition is prepared by adding 0.5part 3-(4- amino-3 -nitroanilino)propionamide (Example 7) to a solutionprepared by mixing 3 parts benzyl alcohol, 5 parts polyethoxylatedoleylammonium chloride, 0.5 part ammonium phosphate, water to make 100parts and heating to 70C. The whole is cooled to ambient temperature.

Virgin albino hair is immersed in this composition for 10 to 15 minutes.The hair is rinsed with water, washed with a dilute shampoo and dried.The hair is dyed a reddish-blue shade.

When this procedure is used for the following nitro compounds of thisinvention, the result on albino hair is as follows:

Compound of Example Color of Dyed Hair 1 bright yellow 3 yellow 7 bluishred 8 bluish red 11 to 15 yellow 28 yellow 30 orange 3 6 red EXAMPLE 40Compound of Example 2 6.0 Sodium sulfite 0.1 lsopropyl alcohol 100 Oleicacid 10.0 Alkyl phenol/ethylene oxide 10.0 condensate Lauric aciddiethanolamide 4.0 Ammonia (28%) 5.0 Water qs to 100.0

When an equal part of 6 percent H is admixed with the above compositionand the resulting solution is applied to yellow grey hair over 20-30minutes, the hair is uniformly dyed a deep brown black.

EXAMPLE 41 Compound of Example 2 4.0 Compound of Example 6 0.2 Compoundof Example 7 0.15 Sodium sulfite 0.1 Oleic acid 10.0 Alkyl phenolethylene oxide 10.0 Lauric acid diethanolamide 4.0 Ammonia (28%) 5.0Water qs to 100.0

When admixed with H 0 and applied to yellow grey hair as in Example 42,this composition uniformly dyes the hair a dark brown.

EXAMPLE 42 Compound of Example 3 4.0 Sodium sulfite 0.1 lsopropylalcohol 10.0 Oleic acid 100 Alkyl phenol ethylene oxide 10.0 Laurie aciddiethanolamide 4.0 Ammonia (28%) 5.0 Water qs to 100.0

When admixed with H 0 and applied to yellow grey hair as in Example 40,this composition uniformly dyes the hair a dark bluish grey.

EXAMPLE 43 Compound of Example 2 5.0 2,4-Dinitro phenol 0.4 p-l-lydroxyanisole 1.0 Sodium sulfite 0.1 lsopropyl alcohol 10.0 Oleic acid 10.0Alkyl phenol ethylene oxide 10.0 Lauric acid diethanolamide 4.0 Ammonia(28%) 5.0 Water qs to [00.0

When admixed with H 0 and applied to albino hair over 15-20 minutes asin Example 40, this composition uniformly dyes the hair a dark drabbrown.

EXAMPLE 44 Compound of Example 2 o-Amino phenol PyrocatecholPhloroglucinol Meta diamino anisol sulfate Sodium sulfite Alkyl phenolethylene oxide lsopropyl alcohol Oleic acid Oleyl alcohol Ammonia (28%)Water qs to 10 When admixed with 11 0 and applied to albino hair as inExample 43, this composition uniformly dyes the hair black.

EXAMPLE 45 When admixed with H 0 and applied to albino hair as inExample 43, this composition uniformly dyes the hair blonde.

EXAMPLE 46 3,3-(p-aminophenylimino)bispropionamide hydrochlorideIIIHrHCl 0 N- omomii-N) A well-stirred mixture of 400 ml. of water, 27.9g. (0.5 m.) of iron powder and 3 m1. of glacial acetic acid is warmed to70C. and there is then added in portions 50.2 g. (0.18 m.) of the3,3-(p-nitrophenylimino)bispropionamide of Example 3. During addition,the temperature rises and is approximately 90C. at the finish. Themixture is stirred at 90-95C. for onehalf hour after the addition iscompleted, cooled to C. and sufficient sodium carbonate added to removeall dissolved iron salts. There is then added activated charcoal and themixture is filtered hot through a diatomaceous earth filter. Thefiltrate is made just acid to Congo Red indicator paper withconcentrated hydrochloric acid and cooled to 0C. The resultingprecipitate is collected by filtration and dried in vacuo at 40C. toyield 36.1 g. (70.3 percent of theory) of3,3-(paminophenylimino)bispropionamide hydrochloride, pinktingedcrystals, rn. 203 204C. This compound when applied in a suitable vehicleto hair, as described in Examples 40 and 43, imparts desirable shadesthereto.

1 claim:

1. A method for dyeing keratinaceous materials which comprisescontacting said material with a compound of the formula lRl Ar -R oracid addition salts thereof where:

Ar is a radical of the benzene, biphenyl or naphthalene series;

Ris Z-carbamoylethylamino or bis(2-carbamoylethyl)- amino;

R is amino, nitro, hydroxy or R; and

, l7 l8 R is hydrogen, chloro, methyl, methoxy, [halo, lower alkox- 5.The method of claim 1 wherein said compound is 3-(5- y ino, nitro or R.amino-o-anisidino)propionamide dihydrochloride.

2. The method of claim 1 wherein said compound is3,3'-(pphenylenediimino)bispropionamide.

F i 1 wherein Said compound is 5 7. The method of claim 1 wherein saidcompound is 3-( 2,4- aminoamlmo)pmplonamlde' dinitroanilino) ro ionamide4. The method of claim 1 wherein said compound is 3-(4- P pamino-B-nitroanilino)propionamide.

v6. The method of claim 1 wherein said compound is 3-(5-amino-o-toluidino)propionamide dihydrochloride.

Patent: No.

(SEAL) Attest:

Attesting Officer EDWARD M.FLETCHE3R,

UNITED STATES PATENT OFFICE Dated Ap 5, 197

Inventor) ALBERT PETER PAUL It is certified that error appea -s in theabove-identified patent and that said Letters Patent are heircbycorrected as shown below:

Column 2, line L B insert tetramino-biphnyl after the numbers "3,3',b,,l

Signed and sealed this Zlflih day of October 1972.

JR. ROBERT GOTTSCHALK Commissioner of Patents F OHM PO-1050 (10-69)USCOMM-DC 60376-1 69 9 IJ.$. GOVIINMINI IRINHIG OFF CE l9. 0-36-334

2. The method of claim 1 wherein said compound is3,3''-(p-phenylenediimino)bispropionamide.
 3. The method of claim 1wherein said compound is 3-(p-aminoanilino)propionamide.
 4. The methodof claim 1 wherein said compound is3-(4-amino-3-nitroanilino)propionamide.
 5. The method of claim 1 whereinsaid compound is 3-(5-amino-o-anisidino)propionamide dihydrochloride. 6.The method of claim 1 wherein said compound is3-(5-amino-o-toluidino)propionamide dihydrochloride.
 7. The method ofclaim 1 wherein said compound is 3-(2,4-dinitroanilino)propionamide.